Positive temperature coefficient film, positive temperature coefficient electrode, positive temperature coefficient separator, and battery comprising the same

ABSTRACT

Provided herein is a positive temperature coefficient film comprising an inorganic positive temperature coefficient compound. Also provided herein are a positive temperature coefficient electrode, a positive temperature coefficient separator, and a positive temperature coefficient lithium secondary battery, each of which comprises the positive temperature coefficient film.

FIELD

Provided herein is a positive temperature coefficient film comprising aninorganic positive temperature coefficient compound. Also providedherein are a positive temperature coefficient electrode, a positivetemperature coefficient separator, and a positive temperaturecoefficient battery, each of which comprises the positive temperaturecoefficient film.

BACKGROUND

Rechargeable lithium batteries, also known as lithium-ion batteries orlithium secondary batteries, are among the most popular rechargeablebatteries for portable electronic devices. Beyond consumer electronics,rechargeable lithium batteries also become popular for military,electronic vehicle, and aerospace applications. One major safety concernwith the current commercial rechargeable lithium batteries is that thebatteries may suffer thermal runaway and cell rupture if overheated orovercharged. Spotnitz and Franklin, J. Power Sources 2003, 113, 81-100.In extreme cases, this can lead to combustion. In 2006, for example,Sony recalled about 6 millions notebook computer batteries after anumber of instances where the batteries overheat or caught fire. Toreduce the risks, rechargeable lithium batteries are commonly equippedwith various safety devices, such as an external positive temperaturecoefficient (PTC) resistor. However, such an external PTC device may notrespond adequately when a hazardous reaction occurs in very high rate,e.g., when an internal short circuit occurs. Thus, there is a greatdemand for rechargeable lithium batteries with an improved safetyprofile, especially rechargeable lithium batteries with high energycapacity. Therefore, there is a need for a PTC electrode for developinga rechargeable lithium battery with an improved safety profile.

SUMMARY OF THE DISCLOSURE

Provided herein is a positive temperature coefficient (PTC) filmcomprising an inorganic PTC compound, a crosslinked polymer, optionallya conductive material, and optionally a filler. In one embodiment, theinorganic PTC compound is in the form of particles, in one embodiment,nanoparticles. In another embodiment, the crosslinked polymer is formedin the presence of the inorganic PTC compound, in one embodiment, in thepresence of nanoparticles of the inorganic PTC compound. In yet anotherembodiment, the positive temperature coefficient (PTC) film furthercomprises a phase transition material and/or a fireretardant material.

Also provided herein is a PTC film comprising no less than about 70% byweight of an inorganic PTC compound, no greater than about 30% by weightof a polymer, and optionally no greater than about 5% by weight of aconductive material. In one embodiment, the inorganic PTC compound is inthe form of particles, in one embodiment, nanoparticles.

Additionally, provided herein is a PTC film comprising an inorganic PTCcompound, a polymer, and optionally a conductive material; wherein thePTC film is formed using water as a solvent.

Furthermore, provided herein is a method for preparing a PTC film thatcomprises an inorganic PTC compound and a crosslinked polymer;comprising the steps of:

(i) coating a mixture of the inorganic PTC compound and the crosslinkedpolymer in a solvent onto at a flat surface to form a wet PTC film; and

(ii) curing the wet PTC film to form the PTC film.

Provided herein is a method for preparing a PTC film that comprises aninorganic PTC compound and a crosslinked polymer; comprising the stepsof:

(i) coating a mixture of the inorganic PTC compound and a precursor ofthe crosslinked polymer, in one embodiment, a crosslinkable polymer, ina solvent onto at a flat surface to form a wet PTC film; and

(ii) curing the wet PTC film by crosslinking the precursor to form thePTC film.

Provided herein is a method for preparing a PTC film comprising aninorganic PTC compound, a polymer, and optionally a conductive material;comprising the steps of:

(i) coating a mixture of the inorganic PTC compound, the polymer, andoptionally the conductive material in water onto at a flat surface toform a wet PTC film; and

(ii) curing the wet PTC film to form the PTC film.

Provided herein is a PTC electrode comprising (i) a current collector;(ii) a PTC film comprising an inorganic PTC compound, a crosslinkedpolymer, optionally a conductive material, and optionally a filler; and(iii) an electroactive material layer.

Provided herein is a PTC electrode comprising (i) a current collector;(ii) a PTC film comprising no less than about 70% by weight of aninorganic PTC compound, no greater than about 30% by weight of apolymer, and optionally no greater than about 5% by weight of aconductive material; and (iii) an electroactive material layer.

Provided herein is a PTC electrode comprising (i) a current collector;(ii) a PTC film comprising an inorganic PTC compound, a polymer, andoptionally a conductive material; and (ii) an electroactive materiallayer; wherein the PTC film is formed using water as s solvent and theelectroactive material layer is formed using an organic solvent.

Provided herein is a PTC electrode comprising (i) a current collector;(ii) a ceramic PTC film comprising an inorganic PTC compound; and (iii)an electroactive material layer.

Provided herein is a method for preparing a PTC electrode that comprisesa current collector, a PTC film comprising an inorganic PTC compound anda crosslinked polymer, and an electroactive material layer; comprisingthe steps of:

(i) coating a mixture of the inorganic PTC compound and the crosslinkedpolymer in a first solvent onto a surface of the current collector toform a wet PTC film;

(ii) curing the wet PTC film to form the PTC film; and

(iii) coating the electroactive material in a second solvent onto thesurface of the PTC film to form the electroactive material layer andthus to form the PTC electrode.

Provided herein is a method for preparing a PTC electrode that comprisesa current collector, a PTC film comprising an inorganic PTC compound anda crosslinked polymer, and an electroactive material layer; comprisingthe steps of:

(i) coating a mixture of the inorganic PTC compound, a precursor of thecrosslinked polymer, in one embodiment, a crosslinkable polymer, in afirst solvent onto a surface of the current collector to form a wet PTCfilm;

(ii) curing the PTC film by crosslinking the precursor to form the PTCfilm; and

(iii) coating the electroactive material in a second solvent onto thesurface of the PTC film to form the electroactive material layer, andthus to form the PTC electrode.

Provided herein is a method for preparing a PTC electrode that comprisesa current collector, a PTC film comprising an inorganic PTC compound anda polymer, and an electroactive material layer; comprising the steps of:

(i) coating a mixture of the inorganic PTC compound and the polymer in afirst solvent onto a surface of the current collector to form the PTCfilm; and

(ii) coating the electroactive material in a second solvent onto thesurface of the PTC film to form the electroactive material layer andthus to form the PTC electrode.

Provided herein is a PTC separator comprising a separator and a PTC filmcomprising an inorganic PTC compound, a crosslinked polymer, optionallya conductive material, and optionally a filler.

Provided herein is a PTC separator comprising a separator and a PTC filmcomprising no less than about 70% by weight of an inorganic PTCcompound, no greater than about 30% by weight of a polymer, andoptionally no greater than about 5% by weight of a conductive material.

Provided herein is a PTC separator comprising a separator and a PTC filmcomprising an inorganic PTC compound, a polymer, and optionally aconductive material; wherein the PTC film is formed using water as ssolvent.

Provided herein is a PTC separator comprising a separator and a ceramicPTC film comprising an inorganic PTC compound.

Provided herein is a battery, in one embodiment, a lithium-secondarybattery, which comprises (i) an anode; (ii) a cathode; (iii) a separatorthat separates the anode and cathode; and (iv) electrolyte; wherein atleast one of the anode and cathode is a PTC electrode; or the separatoris a PTC separator.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic drawing of a PTC electrode comprising a currentcollector 11, a PTC film 12, and an electroactive material layer 13.

FIG. 2 is a schematic drawing of a PTC electrode comprising a currentcollector 11, two PTC films 12, and two electroactive material layers13.

FIG. 3A and FIG. 3B are schematic drawings of two PTC separators: onecomprising a PTC film 12 and a separator 14 (FIG. 3A) and the othercomprising tow PTC films 12 and a separator 14 (FIG. 3B).

FIG. 4 shows voltage, impedance, and temperature profiles of alithium-secondary battery having a PTC cathode as provided herein in anail test.

FIG. 5 shows voltage, impedance, and temperature profiles of alithium-secondary battery having a PTC cathode as provided herein in anail test with a 7 mm diameter nail.

FIG. 6 shows voltage and temperature profiles of a lithium-secondarybattery having a PTC cathode as provided herein in a 2 A/20V overchargetest. No fire and no explosion occurred during the overcharge test.

DETAILED DESCRIPTION

To facilitate understanding of the disclosure set forth herein, a numberof terms are defined below.

Generally, the nomenclature used herein and the laboratory procedures inelectrochemistry, inorganic chemistry, polymer chemistry, organicchemistry, and others described herein are those well known and commonlyemployed in the art. Unless defined otherwise, all technical andscientific terms used herein generally have the same meaning as commonlyunderstood by one of ordinary skill in the art to which this disclosurebelongs.

The term “anode” or “negative electrode” refers to an electrode whereelectrochemical oxidation occurs during discharging process. Forexample, an anode undergoes delithiation during discharging.

The term “cathode” or “positive electrode” refers to an electrode whereelectrochemical reduction occurs during discharging process. Forexample, a cathode undergoes lithiation during discharging.

The term “separator” refers to a porous membrane placed betweenelectrodes of opposite polarity, permeable to ionic flow but preventingelectric contact of the electrodes.

The term “charging” refers to a process of providing electrical energyto an electrochemical cell.

The term “discharging” refers to a process of removing electrical energyfrom an electrochemical cell. In certain embodiments, discharging refersto a process of using the electrochemical cell to do useful work.

The term “electrochemically active,” “electrically active,” and“electroactive” are used interchangeably and refer to a material that iscapable to incorporate lithium in its atomic lattice structure.

The term “lithiation” refers to a chemical process of inserting lithiuminto an electroactive material in an electrochemical cell. In certainembodiments, an electrode undergoes electrochemical reduction duringlithiation process.

The term “delithiation” refers to a chemical process of removing lithiumfrom an electroactive material in an electrochemical cell. In certainembodiments, an electrode undergoes electrochemical oxidation duringdelithiation process.

The term “metal” refers to both metals and metalloids, including siliconand germanium. The phrase “a main group metal” is intended to includeSn, Si, Al, Bi, Ge, and Pb.

The terms “film” and “layer” are used herein interchangeably to refer athin membrane, in one embodiment, a coating on a surface.

The term “about” or “approximately” means an acceptable error for aparticular value as determined by one of ordinary skill in the art,which depends in part on how the value is measured or determined. Incertain embodiments, the term “about” or “approximately” means within 1,2, 3, or 4 standard deviations. In certain embodiments, the term “about”or “approximately” means within 50%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%,4%, 3%, 2%, 1%, 0.5%, or 0.05% of a given value or range.

Positive Temperature Coefficient Films

In one embodiment, provided herein is a PTC film comprising (i) aninorganic PTC compound, in one embodiment, particles of the inorganicPTC compound, in another embodiment, nanoparticles of the inorganic PTCcompound; and (ii) a crosslinked polymer.

In certain embodiments, the inorganic PTC compound is a barium compound,a vanadium compound, a tin compound, a chromium compound or a mixturethereof. In certain embodiments, the inorganic PTC compound is bariumtitanate, a doped barium titanate, vanadium trioxide, a doped vanadiumtrioxide, tin dioxide (SnO₂), chromium oxide (Cr₂O₃), or a mixturethereof. In certain embodiments, the inorganic PTC compound is bariumtitanate or a doped barium titanate. In certain embodiments, theinorganic PTC compound is vanadium trioxide or a doped vanadiumtrioxide. In certain embodiments, the inorganic PTC compound is tindioxide. In certain embodiments, the inorganic PTC compound is chromiumoxide.

In certain embodiments, the inorganic PTC compound is a barium compound.In certain embodiments, the inorganic PTC compound is a barium salt. Incertain embodiments, the inorganic PTC compound comprises bariumtitanate. In certain embodiments, the inorganic PTC compound is bariumtitanate.

In certain embodiments, the inorganic PTC compound comprises a dopedbarium titanate. In certain embodiments, the inorganic PTC compound is adoped barium titanate. In certain embodiments, the doped barium titanateis made by doping metal or material with a low-resistance phase intobarium titanate. In certain embodiments, the metal doped into bariumtitanate is lanthanum, antimony, yttrium, niobium, tantalum, nickel, ora combination thereof. In certain embodiments, the doped barium titanateis (Ba_(1-v-w)M_(v)Sr_(w))Ti_(x)O₃+ySiO₂; wherein M is Er, Sm, Ce, La,or a combination thereof; 0.005≧v≧0.001; 0.49≧w≧0.42; 1.03≧x≧0.99; and0.030≧y≧0.002. Examples of suitable barium compounds include those asdescribed in U.S. Pat. App. Pub. No. 2012/0068127, the disclosure ofwhich is incorporated herein by reference in its entirety. In certainembodiments, the doped barium titanate is(Ba_(1-x)M_(x))_(z)(Ti_(1-y)O₃R_(y))O₃; wherein M is Y, La, Ce, Pr, Nd,Sm, Gd, Dy, Er, Sm, Ce, La, or a combination thereof; R is V, Nb, Ta, ora combination thereof; 0.003≧x≧0.001; 0.002≧y≧0, and 1.1≧z≧0.99.Examples of suitable barium compounds include those as described in U.S.Pat. App. Pub. No. 2012/0056709, the disclosure of which is incorporatedherein by reference in its entirety.

In certain embodiments, the inorganic PTC compound is a vanadiumcompound. In certain embodiments, the inorganic PTC compound is avanadium oxide. In certain embodiments, the inorganic PTC compoundcomprises vanadium trioxide. In certain embodiments, the inorganic PTCcompound is vanadium trioxide (V₂O₃).

In certain embodiments, the inorganic PTC compound is a doped vanadiumtrioxide. In certain embodiments, the doped V₂O₃ is made by doping metalor material with a low-resistance phase into V₂O₃. In certainembodiments, the metal doped into V₂O₃ is lanthanum, antimony, yttrium,niobium, tantalum, nickel, or a combination thereof.

In certain embodiments, the inorganic PTC compound is in the form ofparticles. In certain embodiments, the inorganic PTC compound is in theform of micrometer-sized particles. In certain embodiments, theinorganic PTC compound is in the form of nanoparticles. In certainembodiments, the inorganic PTC compound has an average particle sizeranging from about 1 to about 1,000 nm, from about 2 to about 500 nm,from about 5 to about 500 nm, from about 10 to about 250 nm, from about20 to about 250 nm, from about 50 to about 250 nm, or from about 100 toabout 200 nm.

In certain embodiments, the inorganic PTC compound has an averageparticle size ranging from about 10 to about 250 nm. In certainembodiments, the inorganic PTC compound has an average particle sizeranging from about 10 to about 100 nm. In certain embodiments, theinorganic PTC compound has an average particle size ranging from about10 to about 50 nm. In certain embodiments, the inorganic PTC compoundhas an average particle size ranging from about 10 to about 20 nm.

In certain embodiments, the inorganic PTC compound has an averageparticle size ranging from about 20 to about 250 nm. In certainembodiments, the inorganic PTC compound has an average particle sizeranging from about 20 to about 100 nm. In certain embodiments, theinorganic PTC compound has an average particle size ranging from about20 to about 50 nm.

In certain embodiments, the inorganic PTC compound has an averageparticle size ranging from about 50 to about 250 nm. In certainembodiments, the inorganic PTC compound has an average particle sizeranging from about 50 to about 200 nm. In certain embodiments, theinorganic PTC compound has an average particle size ranging from about100 to about 200 nm.

In certain embodiments, the inorganic PTC compound has an averageparticle size of about 10, about 20, about 30, about 40, about 50, about75, about 100, about 150, about 200, about 300, about 400, or about 500nm.

In certain embodiments, the crosslinked polymer is a crosslinkedpolybenzophenone, a crosslinked polyacrylate, a crosslinked polyvinyl, acrosslinked polyethylene, a crosslinked polypropylene, a crosslinkedpolystyrene, a crosslinked polysulfone, a crosslinked2,3-dihydrofuran-containing polymer, a crosslinked carboxymethylcellulose (CMC), a crosslinked polyamide-imide, a crosslinked polyimide,a crosslinked styrene-containing copolymer, or a mixture thereof.

In certain embodiments, the crosslinked polymer is a crosslinkedpolybenzophenone. In certain embodiments, the crosslinked polymer is acrosslinked polyacrylate. In certain embodiments, the crosslinkedpolymer is a crosslinked polyvinyl. In certain embodiments, thecrosslinked polymer is a crosslinked polyethylene. In certainembodiments, the crosslinked polymer is a crosslinked polypropylene. Incertain embodiments, the crosslinked polymer is a crosslinkedpolystyrene. In certain embodiments, the crosslinked polymer is acrosslinked polysulfone. In certain embodiments, the crosslinked polymeris a crosslinked 2,3-dihydrofuran-containing polymer. In certainembodiments, the crosslinked polymer is a crosslinked carboxymethylcellulose. In certain embodiments, the crosslinked polymer is acrosslinked polyamide-imide. In certain embodiments, the crosslinkedpolymer is a crosslinked polyimide. In certain embodiments, thecrosslinked polymer is a crosslinked styrene-containing copolymer.

In certain embodiments, the crosslinked polymer is a thermallycrosslinked polymer. In certain embodiments, the crosslinked polymer isa thermally crosslinked CMC, a thermally crosslinked polyamide-imide, athermally crosslinked polyimide, or a mixture thereof. In certainembodiments, the crosslinked polymer is a thermally crosslinked CMC. Incertain embodiments, the crosslinked polymer is a thermally crosslinkedpolyamide-imide. In certain embodiments, the crosslinked polymer is athermally crosslinked polyimide.

In certain embodiments, the crosslinked polymer is a photo-crosslinkedpolymer.

In certain embodiments, the crosslinked polymer is a photo-crosslinkedpolybenzophenone, a photo-crosslinked polyacrylate, a photo-crosslinkedpolyvinyl, a photo-crosslinked polystyrene, a photo-crosslinkedpolysulfone, a photo-crosslinked 2,3-dihydrofuran-containing polymer, aphoto-crosslinked styrene-containing copolymer, or a mixture thereof. Incertain embodiments, the crosslinked polymer is a photo-crosslinkedpolybenzophenone. In certain embodiments, the crosslinked polymer is aphoto-crosslinked polyacrylate. In certain embodiments, the crosslinkedpolymer is a photo-crosslinked polyvinyl. In certain embodiments, thecrosslinked polymer is a photo-crosslinked polystyrene. In certainembodiments, the crosslinked polymer is a photo-crosslinked polysulfone.In certain embodiments, the crosslinked polymer is a photo-crosslinked2,3-dihydrofuran-containing polymer. In certain embodiments, thecrosslinked polymer is a photo-crosslinked styrene-containing copolymer.

In certain embodiments, the crosslinked polymer is a crosslinked PTCpolymer. In certain embodiments, the crosslinked PTC polymer is acrosslinked polyethylene, a crosslinked polypropylene, or a mixturethereof. In certain embodiments, the crosslinked PTC polymer is acrosslinked high-density polyethylene, a crosslinked low-densitypolyethylene, a crosslinked high-density polypropylene, a crosslinkedlow-density polypropylene, or a mixture thereof.

In one embodiment, the crosslinked polymer is formed in the presence ofthe inorganic PTC compound. In another embodiment, the crosslinkedpolymer is formed in the presence of the particles of the inorganic PTCcompound.

In certain embodiments, the crosslinked polymer is formed from one ormore precursors of the crosslinked polymer. In certain embodiments, theprecursor of the crosslinked polymer is a crosslinkable polymer. Incertain embodiments, the precursor of the crosslinked polymer is amonomer.

In certain embodiments, the crosslinked polymer is formed bycrosslinking one or more crosslinkable polymers. In certain embodiments,the crosslinkable polymer is a crosslinkable polybenzophenone, acrosslinkable polyacrylate, a crosslinkable polyvinyl, a crosslinkablepolyethylene, a crosslinkable polypropylene, a crosslinkablepolystyrene, a crosslinkable polysulfone, a crosslinkable2,3-dihydrofuran-containing polymer, a crosslinkable carboxymethylcellulose, a crosslinkable polyamide-imide, a crosslinkable polyimide, acrosslinkable styrene-containing copolymer, or a mixture thereof.

In certain embodiments, the crosslinkable polymer is a crosslinkablepolybenzophenone. In certain embodiments, the crosslinkable polymer is acrosslinkable polyacrylate. In certain embodiments, the crosslinkablepolymer is a crosslinkable polyvinyl. In certain embodiments, thecrosslinkable polymer is a crosslinkable polyethylene. In certainembodiments, the crosslinkable polymer is a crosslinkable polypropylene.In certain embodiments, the crosslinkable polymer is a crosslinkablepolystyrene. In certain embodiments, the crosslinkable polymer is acrosslinkable polysulfone. In certain embodiments, the crosslinkablepolymer is a crosslinkable 2,3-dihydrofuran-containing polymer. Incertain embodiments, the crosslinkable polymer is a crosslinkablecarboxymethyl cellulose, a crosslinkable polyamide-imide. In certainembodiments, the crosslinkable polymer is a crosslinkable polyimide. Incertain embodiments, the crosslinkable polymer is a crosslinkablestyrene-containing copolymer.

In certain embodiments, the crosslinkable polymer is a thermallycrosslinkable polymer. In certain embodiments, the crosslinkable polymeris a thermally crosslinkable CMC, a thermally crosslinkablepolyamide-imide, a thermally crosslinkable polyimide, or a mixturethereof. In certain embodiments, the crosslinkable polymer is athermally crosslinkable CMC. In certain embodiments, the crosslinkablepolymer is a thermally crosslinkable polyamide-imide. In certainembodiments, the crosslinkable polymer is a thermally crosslinkablepolyimide.

In certain embodiments, the crosslinkable polymer is aphoto-crosslinkable polymer. In certain embodiments, the crosslinkablepolymer is a photo-crosslinkable polybenzophenone, a photo-crosslinkablepolyacrylate, a photo-crosslinkable polyvinyl, a photo-crosslinkablepolystyrene, a photo-crosslinkable polysulfone, a photo-crosslinkable2,3-dihydrofuran-containing polymer, a photo-crosslinkablestyrene-containing copolymer, or a mixture thereof. In certainembodiments, the crosslinkable polymer is a photo-crosslinkable polymer.In certain embodiments, the crosslinkable polymer is aphoto-crosslinkable polybenzophenone. In certain embodiments, thecrosslinkable polymer is a photo-crosslinkable polyacrylate. In certainembodiments, the crosslinkable polymer is a photo-crosslinkablepolyvinyl. In certain embodiments, the crosslinkable polymer is aphoto-crosslinkable polystyrene. In certain embodiments, thecrosslinkable polymer is a photo-crosslinkable polysulfone. In certainembodiments, the crosslinkable polymer is a photo-crosslinkable2,3-dihydrofuran-containing polymer. In certain embodiments, thecrosslinkable polymer is a photo-crosslinkable styrene-containingcopolymer.

In certain embodiments, the crosslinkable polymer is a crosslinkable PTCpolymer. In certain embodiments, the crosslinkable PTC polymer is acrosslinkable polyethylene, a crosslinkable polypropylene, or a mixturethereof. In certain embodiments, the crosslinkable PTC polymer is acrosslinkable high-density polyethylene, a crosslinkable low-densitypolyethylene, a crosslinkable high-density polypropylene, acrosslinkable low-density polypropylene, or a mixture thereof.

In one embodiment, the crosslinkable polymer is a polyamide-imide,polyimide, or a mixture thereof. In certain embodiments, thepolyamide-imide is aromatic, aliphatic, cycloaliphatic, or a mixturethereof. In certain embodiments, the polyamide-imide is an aromaticpolyamide-imide. In certain embodiments, the polyamide-imide is analiphatic polyamide-imide. In certain embodiments, the polyamide-imideis a cycloaliphatic polyamide-imide. In certain embodiments, thepolyimide is aromatic, aliphatic, cycloaliphatic, or a mixture thereof.In certain embodiments, the polyimide is an aromatic polyimide. Incertain embodiments, the polyimide is an aliphatic polyimide. In certainembodiments, the polyimide is a cycloaliphatic polyimide.

In certain embodiments, the crosslinkable polymer is TORLON® AI-30,TORLON® AI-50, TORLON® 4000, TORLON® 4203L, or a mixture thereof (SolvayAdvanced Polymers, L.L.C., Ao0yaretta, GA). In certain embodiments, thecrosslinkable polymer is TORLON® AI-30. In certain embodiments, thecrosslinkable polymer is TORLON® AI-50. In certain embodiments, thecrosslinkable polymer is TORLON® 4000. In certain embodiments, thecrosslinkable polymer is TORLON® 4203L.

Example of suitable polyamide-imide and polyimides include thosedescribed in Loncrini and Witzel, Journal of Polymer Science Part A-1:Polymer Chemistry 1969, 7, 2185-2193; Jeon and Tak, Journal of AppliedPolymer Science 1996, 60, 1921-1926; Seino et al., Journal of PolymerScience Part A: Polymer Chemistry 1999, 37, 3584-3590; Seino et al.,High Performance Polymers 1999, 11, 255-262; Matsumoto, High PerformancePolymers 2001, 13, S85-S92; Schab-Balcerzak et al., European PolymerJournal 2002, 38, 423-430; Eichstadt et al., Journal of Polymer SciencePart B: Polymer Physics 2002, 40, 1503-1512; and Fang et al., Polymer2004, 45, 2539-2549; the disclosure of each of which is incorporatedherein by reference in its entirety.

In certain embodiments, the precursors of the crosslinkedpolyamide-imide are a polyanhydride and polyamine. In certainembodiments, the crosslinked polyamide-imide is formed from apolyanhydride and a polyamine via polymerization in the presence of aninorganic PTC compound, in one embodiment, particles of the inorganicPTC compound.

In certain embodiments, the precursors of the crosslinked polyimide area polyanhydride and polyamine. In certain embodiments, the crosslinkedpolyimide is formed from a polyanhydride and a polyamine viapolymerization in the presence of an inorganic PTC compound, in oneembodiment, particles of the inorganic PTC compound.

Suitable polyanhydrides, polyamines, polyamide-imide, and polyimidesinclude those described in Eur. Pat. App. Pub. Nos. EP 0450549 and EP1246280; U.S. Pat. No. 5,504,128; and U.S. Pat. App. Pub. Nos.2006/0099506 and 2007/0269718, the disclosure of each of which isincorporated herein by reference in its entirety.

Suitable polyanhydrides include, but are not limited to,butanetetracarboxylic dianhydride, meso-1,2,3,4-butanetetracarboxylicdianhydride, dl-1,2,3,4-butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylicdianhydride, cyclohexane tetracarboxylic dianhydride,1,2,3,4-cyclohexanetetracarboxylic dianhydride,cis-1,2,3,4-cyclohexanetetracarboxylic dianhydride,trans-1,2,3,4-cyclohexanetetracarboxylic dianhydride,bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic 2,3:5,6-dianhydride,bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride,bicyclo[2.2.1]-heptane-2,3,5,6-tetracarboxylic 2,3:5,6-dianhydride,(4arH, 8acH)-decahydro-1,t,4t:5c,4-cyclohexene-1,1,2,2-tetracarboxylic1,2:1,2-dianhydride,bicyclo[2.2.1]heptane-2-exo-3-exo-5-exo-tricarboxyl-5-endo-aceticdianhydride, bicyclo[4.2.0]oxetane-1,6,7,8-tetracarboxylic acidintramolecular dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylicdianhydride, 4,4′-hexafluoropropylidene bisphthalic dianhydride,1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane, andcombinations thereof.

Suitable polyamines include, but are not limited to,4,4′-methylenebis(2,6-dimethylaniline), 4,4′-oxydianiline,m-phenylenediamine, p-phenylenediamine, benzidene, 3,5-diaminobenzoicacid, o-dianisidine, 4,4′-diaminodiphenyl methane,4,4′-methylenebis(2,6-dimethylaniline), 1,4-diaminobutane,1,6-diaminohexane, 1,7-diaminoheptane, 1,9-diaminononane,1,10-diaminodecane, 1,12-diaminododecane,5-amino-1,3,3-trimethylcyclohexanemethylamine,2,5-bis(aminomethyl)bicyclo[2.2.1]heptane,2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,4-diaminotoluene,1,4-diamino-2-methoxybenzene, 1,4-diamino-2-phenylbenzene and1,3-diamino-4-chlorobenzene, 4,4′-diaminobiphenyl,2,2-bis(4-aminophenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane,2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane,2,2-bis(4-aminophenoxyphenyl)hexafluoropropane, 4,4′-diaminodiphenylether, 3,4-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene,1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene,4,4′-bis(4-aminophenoxy)biphenyl, 4,4′-bis(3-aminophenoxy)biphenyl,2,2-bis[4-(4-aminophenoxy)phenyl]propane,2,2-bis[4-(4-aminophenoxy)phenyl]propane,2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,4,4′-diaminodiphenylthioether, 4,4′-diaminodiphenyl sulfone,2,2′-diaminobenzophenone, 3,3′-diaminobenzophenone, naphthalene diamines(including 1,8-diaminonaphthalene and 1,5-diaminonaphthalene),2,6-diaminopyridine, 2,4-diaminopyrimidine, 2,4-diamino-s-triazine,1,8-diamino-4-(aminomethyl)octane,bis[4-(4-aminophenoxy)-phenyl]sulfone,3,3′-dihydroxy-4,4′-diaminobiphenyl,2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane,2,2-bis(3-hydroxy-4-aminophenyl)propane, and combinations thereof.

In certain embodiments, the crosslinked polymer is a polyimide formedfrom U-VARNISH® (UBE American Inc., New York, N.Y.).

In certain embodiments, the PTC film comprises no less than about 50%,no less than about 55%, no less than about 60%, no less than about 65%,no less than about 70%, no less than about 75%, no less than about 80%,no less than about 85%, no less than about 90%, or no less than about95% by weight of the inorganic PTC compound. In certain embodiments, thePTC film comprises no less than about 60%, no less than about 65%, noless than about 70%, no less than about 75%, no less than about 80%, noless than about 85%, or no less than about 90% by weight of theinorganic PTC compound. In certain embodiments, the PTC film comprisesabout 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about80%, about 85%, about 90%, or about 95% by weight of the inorganic PTCcompound. In certain embodiments, the PTC film comprises about 70%,about 75%, about 80%, about 85%, about 90%, or about 95% by weight ofthe inorganic PTC compound.

In certain embodiments, the PTC film comprises no greater than about50%, no greater than about 45%, no greater than about 40%, no greaterthan about 35%, no greater than about 30%, no greater than about 25%, nogreater than about 20%, no greater than about 15%, no greater than about10%, or no greater than about 5% by weight of the crosslinked polymer.In certain embodiments, the PTC film comprises no greater than about40%, no greater than about 35%, no greater than about 30%, no greaterthan about 25%, no greater than about 20%, no greater than about 15%, orno greater than about 10% by weight of the crosslinked polymer. Incertain embodiments, the PTC film comprises about 50%, about 45%, about40%, about 35%, about 30%, about 25%, about 20%, about 15%, about 10%,or about 5% by weight of the crosslinked polymer. In certainembodiments, the PTC film comprises about 35%, about 30%, about 25%,about 20%, about 15%, about 10%, or about 5% by weight of thecrosslinked polymer.

In certain embodiments, the PTC film comprises no less than about 50% byweight of the inorganic PTC compound and no greater than about 50% byweight of the crosslinked polymer. In certain embodiments, the PTC filmcomprises no less than about 55% by weight of the inorganic PTC compoundand no greater than about 45% by weight of the crosslinked polymer. Incertain embodiments, the PTC film comprises no less than about 60% byweight of the inorganic PTC compound and no greater than about 40% byweight of the crosslinked polymer. In certain embodiments, the PTC filmcomprises no less than about 65% by weight of the inorganic PTC compoundand no greater than about 35% by weight of the crosslinked polymer. Incertain embodiments, the PTC film comprises no less than about 70% byweight of the inorganic PTC compound and no greater than about 30% byweight of the crosslinked polymer. In certain embodiments, the PTC filmcomprises no less than about 75% by weight of the inorganic PTC compoundand no greater than about 25% by weight of the crosslinked polymer. Incertain embodiments, the PTC film comprises no less than about 80% byweight of the inorganic PTC compound and no greater than about 20% byweight of the crosslinked polymer. In certain embodiments, the PTC filmcomprises no less than about 85% by weight of the inorganic PTC compoundand no greater than about 15% by weight of the crosslinked polymer. Incertain embodiments, the PTC film comprises no less than about 90% byweight of the inorganic PTC compound and no greater than about 10% byweight of the crosslinked polymer. In certain embodiments, the PTC filmcomprises no less than about 95% by weight of the inorganic PTC compoundand no greater than about 5% by weight of the crosslinked polymer.

In certain embodiments, the PTC film has a thickness ranging from about100 nm to about 200 μm, from about 500 nm to about 100 μm, from about 1to about 100 μm, from about 1 to about 50 μm, from about 2 to about 50μm, from about 5 to about 50 μm, from about 10 to about 50 μm, or fromabout 10 to about 50 μm. In certain embodiments, the PTC film has athickness of about 2, about 5, about 10, about 20, about 30, about 40,or about 50 μm.

In certain embodiments, the PTC film has a two-dimensional densityranging from about 0.01 to about 100 mg/cm², from about 0.05 to about 50mg/cm², from about 0.1 to about 25 mg/cm², from about 0.2 to about 10mg/cm², from about 0.5 to about 5 mg/cm², from about 0.5 to about 5mg/cm², or from about 0.5 to about 2 mg/cm². In certain embodiments, thePTC film has a loading of about 0.1 mg/cm², about 0.25 mg/cm², about 0.5mg/cm², about 1 mg/cm², about 1.5 mg/cm², about 2 mg/cm², or about 5mg/cm².

In one embodiment, the PTC film comprises barium titanate and acrosslinked polyamide-imide. In another embodiment, the PTC filmcomprises no less than about 50% by weight of barium titanate and nogreater than about 50% by weight of the crosslinked polyamide-imide. Inyet another embodiment, the PTC film comprises no less than about 60% byweight of barium titanate and no greater than about 40% by weight of thecrosslinked polyamide-imide. In yet another embodiment, the PTC filmcomprises no less than about 70% by weight of barium titanate and nogreater than about 30% by weight of the crosslinked polyamide-imide. Inyet another embodiment, the PTC film comprises no less than about 75% byweight of barium titanate and no greater than about 25% by weight of thecrosslinked polyamide-imide. In yet another embodiment, the PTC filmcomprises no less than about 80% by weight of barium titanate and nogreater than about 20% by weight of the crosslinked polyamide-imide. Instill another embodiment, the PTC film comprises no less than about 85%by weight of barium titanate and no greater than about 15% by weight ofthe crosslinked polyamide-imide.

In one embodiment, the PTC film comprises about 70% by weight of bariumtitanate and about 30% by weight of the crosslinked polyamide-imide. Inanother embodiment, the PTC film comprises about 75% by weight of bariumtitanate and about 25% by weight of the crosslinked polyamide-imide. Inyet another embodiment, the PTC film comprises about 80% by weight ofbarium titanate and about 20% by weight of the crosslinkedpolyamide-imide. In yet another embodiment, the PTC film comprises about85% by weight of barium titanate and about 15% by weight of thecrosslinked polyamide-imide. In yet another embodiment, the PTC filmcomprises about 90% by weight of barium titanate and about 10% by weightof the crosslinked polyamide-imide. In still another embodiment, the PTCfilm comprises about 95% by weight of barium titanate and about 5% byweight of the crosslinked polyamide-imide.

In one embodiment, the PTC film comprises barium titanate and acrosslinked polypropylene. In another embodiment, the PTC film comprisesno less than about 50% by weight of barium titanate and no greater thanabout 50% by weight of the crosslinked polypropylene. In yet anotherembodiment, the PTC film comprises no less than about 60% by weight ofbarium titanate and no greater than about 40% by weight of thecrosslinked polypropylene. In yet another embodiment, the PTC filmcomprises no less than about 70% by weight of barium titanate and nogreater than about 30% by weight of the crosslinked polypropylene. Inyet another embodiment, the PTC film comprises no less than about 75% byweight of barium titanate and no greater than about 25% by weight of thecrosslinked polypropylene. In yet another embodiment, the PTC filmcomprises no less than about 80% by weight of barium titanate and nogreater than about 20% by weight of the crosslinked polypropylene. Inyet another embodiment, the PTC film comprises no less than about 85% byweight of barium titanate and no greater than about 15% by weight of thecrosslinked polypropylene.

In one embodiment, the PTC film comprises about 70% by weight of bariumtitanate and about 30% by weight of the crosslinked polypropylene. Inanother embodiment, the PTC film comprises about 75% by weight of bariumtitanate and about 25% by weight of the crosslinked polypropylene. Inyet another embodiment, the PTC film comprises about 80% by weight ofbarium titanate and about 20% by weight of the crosslinkedpolypropylene. In yet another embodiment, the PTC film comprises about85% by weight of barium titanate and about 15% by weight of thecrosslinked polypropylene. In yet another embodiment, the PTC filmcomprises about 90% by weight of barium titanate and about 10% by weightof the crosslinked polypropylene. In still another embodiment, the PTCfilm comprises about 95% by weight of barium titanate and about 5% byweight of the crosslinked polypropylene.

In certain embodiments, the PTC film further comprises a conductivematerial, a phase transition material, and/or a fireretardant material.Suitable phase transition materials include, but are not limited to,paraffin, PEG, paraffin wax, and dry organic materials. Suitablefireretardant materials include, but are not limited to, (i) inorganiccompounds that can release CO₂, e.g., Li₂CO₃, CaCO₃, and Na₂CO₃; (ii)borates, e.g., Mg₂B₂O₅ and Li₆B₄O₉; and (iii) orgranophosphates, e.g.,triphenyl phosphate and bisphenol A diphenyl phosphate (BADP).

In certain embodiments, the PTC film further comprises a conductivematerial. Thus, in one embodiment, provided herein is a PTC filmcomprising (i) an inorganic PTC compound, in one embodiment, particlesof the inorganic PTC compound; (ii) a crosslinked polymer; and (iii) aconductive material, in one embodiment, particles of the conductivematerial.

In certain embodiments, the conductive material is carbon. In certainembodiments, the conductive material is acetylene black, ketjen black,furnace black, lamp black, carbon, disordered carbon, carbon black,graphite, graphene, a carbon nanotube, a single-walled nanotube, amulti-wall nanotube, a carbon fiber, or a mixture thereof. In certainembodiments, the conductive material is carbon black.

In certain embodiments, the conductive material is a metal, in oneembodiment, metal particles. In certain embodiments, the conductivematerial is aluminum, chromium, copper, cobalt, gold, iron, lead,molybdenum, nickel, platinum, silver, titanium, tungsten, or acombination thereof.

In certain embodiments, the conductive material is a conductive polymer.In certain embodiments, the conductive material is polythiophene,poly(3-hexylthiophene), poly(2-acetylthiophene), polybenzothiopnene,poly(2,5-dimethylthiophene), poly(2-ethylthiophene), poly(3-carboxylicethyl thiophene), polythiopheneacetonitrile,poly(3,4-ethylenedioxythiophene), polyisothianaphthene, polypyrrole,polyaniline, polyparaphenylene, or a combination thereof.

The conductive material used herein is not limited by its shape. Incertain embodiments, the conductive material is sphere, fibril, fiber,or platelet.

In certain embodiments, the PTC film comprises no greater than about20%, no greater than about 10%, no greater than about 5%, no greaterthan about 4%, no greater than about 3%, no greater than about 2%, or nogreater than about 1% by weight of the conductive material. In certainembodiments, the PTC film comprises about 1%, about 2%, about 3%, about4%, or about 5% by weight of the conductive material. In certainembodiments, the PTC film comprises about 1% by weight of the conductivematerial.

In certain embodiments, the PTC film comprises no less than about 50% byweight of the inorganic PTC compound, no greater than about 50% byweight of the crosslinked polymer, and no greater than about 5% byweight of the conductive material. In certain embodiments, the PTC filmcomprises no less than about 55% by weight of the inorganic PTCcompound, no greater than about 45% by weight of the crosslinkedpolymer, and no greater than about 5% by weight of the conductivematerial. In certain embodiments, the PTC film comprises no less thanabout 60% by weight of the inorganic PTC compound, no greater than about40% by weight of the crosslinked polymer, and no greater than about 5%by weight of the conductive material. In certain embodiments, the PTCfilm comprises no less than about 65% by weight of the inorganic PTCcompound, no greater than about 35% by weight of the crosslinkedpolymer, and no greater than about 5% by weight of the conductivematerial. In certain embodiments, the PTC film comprises no less thanabout 70% by weight of the inorganic PTC compound, no greater than about30% by weight of the crosslinked polymer, and no greater than about 5%by weight of the conductive material. In certain embodiments, the PTCfilm comprises no less than about 75% by weight of the inorganic PTCcompound, no greater than about 25% by weight of the crosslinkedpolymer, and no greater than about 5% by weight of the conductivematerial. In certain embodiments, the PTC film comprises no less thanabout 80% by weight of the inorganic PTC compound, no greater than about20% by weight of the crosslinked polymer, and no greater than about 5%by weight of the conductive material. In certain embodiments, the PTCfilm comprises no less than about 85% by weight of the inorganic PTCcompound, no greater than about 15% by weight of the crosslinkedpolymer, and no greater than about 5% by weight of the conductivematerial. In certain embodiments, the PTC film comprises no less thanabout 90% by weight of the inorganic PTC compound, no greater than about10% by weight of the crosslinked polymer, and no greater than about 2%by weight of the conductive material. In certain embodiments, the PTCfilm comprises no less than about 95% by weight of the inorganic PTCcompound, no greater than about 5% by weight of the crosslinked polymer,and no greater than about 2% by weight of the conductive material.

In one embodiment, the PTC film comprises barium titanate, a crosslinkedpolyamide-imide, and carbon black. In another embodiment, the PTC filmcomprises no less than about 50% by weight of barium titanate, nogreater than about 50% by weight of the crosslinked polyamide-imide, andno greater than about 5% of carbon black. In yet another embodiment, thePTC film comprises no less than about 60% by weight of barium titanate,no greater than about 40% by weight of the crosslinked polyamide-imide,and no greater than about 5% of carbon black. In yet another embodiment,the PTC film comprises no less than about 70% by weight of bariumtitanate, no greater than about 30% by weight of the crosslinkedpolyamide-imide, and no greater than about 5% of carbon black. In yetanother embodiment, the PTC film comprises no less than about 75% byweight of barium titanate, no greater than about 25% by weight of thecrosslinked polyamide-imide, and no greater than about 5% of carbonblack. In yet another embodiment, the PTC film comprises no less thanabout 80% by weight of barium titanate, no greater than about 20% byweight of the crosslinked polyamide-imide, and no greater than about 2%of carbon black. In still another embodiment, the PTC film comprises noless than about 85% by weight of barium titanate, no greater than about15% by weight of the crosslinked polyamide-imide, and no greater thanabout 2% of carbon black.

In one embodiment, the PTC film comprises barium titanate, a crosslinkedpolypropylene, and carbon black. In another embodiment, the PTC filmcomprises no less than about 50% by weight of barium titanate, nogreater than about 50% by weight of the crosslinked polypropylene, andno greater than about 5% of carbon black. In yet another embodiment, thePTC film comprises no less than about 60% by weight of barium titanate,no greater than about 40% by weight of the crosslinked polypropylene,and no greater than about 5% of carbon black. In yet another embodiment,the PTC film comprises no less than about 70% by weight of bariumtitanate, no greater than about 30% by weight of the crosslinkedpolypropylene, and no greater than about 5% of carbon black. In yetanother embodiment, the PTC film comprises no less than about 75% byweight of barium titanate, no greater than about 25% by weight of thecrosslinked polypropylene, and no greater than about 5% of carbon black.In yet another embodiment, the PTC film comprises no less than about 80%by weight of barium titanate, no greater than about 20% by weight of thecrosslinked polypropylene, and no greater than about 2% of carbon black.In still another embodiment, the PTC film comprises no less than about85% by weight of barium titanate, no greater than about 15% by weight ofthe crosslinked polypropylene, and no greater than about 2% of carbonblack.

In certain embodiments, the PTC film further comprises a filler. Thus,in one embodiment, provided herein is a PTC film comprising (i) aninorganic PTC compound, in one embodiment, particles of the inorganicPTC compound; (ii) a crosslinked polymer; (iii) a conductive material,in one embodiment, particles of the conductive material; and (iv) afiller, in one embodiment, a binder.

In certain embodiments, the filler is asphalt pitch, pitch coke,petroleum coke, a sugar (e.g., sucrose), coal tar, fluoranthene, pyrene,chrysene, phenanthrene, anthracene, naphthalin, fluorene, biphenyl,acenephthene, a solid ionic conductor, a polyamide-imide, a polyimide,polytetrafluoroethylene (PTFE), CMC, polyvinylidene fluoride (PVDF),polyvinyl alcohol (PVA), styrene butadiene rubber (SBR), or a mixturethereof. In certain embodiments, the filler is a polymer. In certainembodiments, the polymeric filler is a polyamide-imide, a polyimide,PTFE, CMC, PVDF, PVA, SBR, or a mixture thereof. In certain embodiments,the filler is PVDF, SBR, or a mixture thereof. In certain embodiments,the filler is PVDF. In certain embodiments, the filler is SBR.

In certain embodiments, the PTC film comprises no greater than about50%, no greater than about 40%, no greater than about 30%, no greaterthan about 25%, no greater than about 10%, no greater than about 15%, nogreater than about 10%, or no greater than about 5% by weight of thefiller. In certain embodiments, the PTC film comprises about 30%, about25%, about 20%, about 15%, about 10%, or about 5% by weight of thefiller. In certain embodiments, the PTC film comprises about 5%, about5.5%, about 6%, about 6.5%, about 7.5%, about 8%, about 8.5%, about 9%,about 9.5%, or 10% by weight of the filler.

In certain embodiments, the PTC film comprises no less than about 50% byweight of the inorganic PTC compound, no greater than about 50% byweight of the crosslinked polymer, no greater than about 5% by weight ofthe conductive material, and no greater than about 30% by weight of thefiller. In certain embodiments, the PTC film comprises no less thanabout 55% by weight of the inorganic PTC compound, no greater than about45% by weight of the crosslinked polymer, no greater than about 5% byweight of the conductive material, and no greater than about 10% byweight of the filler. In certain embodiments, the PTC film comprises noless than about 60% by weight of the inorganic PTC compound, no greaterthan about 40% by weight of the crosslinked polymer, no greater thanabout 5% by weight of the conductive material, and no greater than about10% by weight of the filler. In certain embodiments, the PTC filmcomprises no less than about 65% by weight of the inorganic PTCcompound, no greater than about 35% by weight of the crosslinkedpolymer, no greater than about 5% by weight of the conductive material,and no greater than about 10% by weight of the filler. In certainembodiments, the PTC film comprises no less than about 70% by weight ofthe inorganic PTC compound, no greater than about 30% by weight of thecrosslinked polymer, no greater than about 5% by weight of theconductive material, and no greater than about 10% by weight of thefiller. In certain embodiments, the PTC film comprises no less thanabout 75% by weight of the inorganic PTC compound, no greater than about25% by weight of the crosslinked polymer, no greater than about 5% byweight of the conductive material, and no greater than about 10% byweight of the filler. In certain embodiments, the PTC film comprises noless than about 80% by weight of the inorganic PTC compound, no greaterthan about 20% by weight of the crosslinked polymer, no greater thanabout 5% by weight of the conductive material, and no greater than about10% by weight of the filler. In certain embodiments, the PTC filmcomprises no less than about 85% by weight of the inorganic PTCcompound, no greater than about 15% by weight of the crosslinkedpolymer, no greater than about 5% by weight of the conductive material,and no greater than about 10% by weight of the filler. In certainembodiments, the PTC film comprises no less than about 90% by weight ofthe inorganic PTC compound, no greater than about 10% by weight of thecrosslinked polymer, no greater than about 2% by weight of theconductive material, and no greater than about 10% by weight of thefiller. In certain embodiments, the PTC film comprises no less thanabout 95% by weight of the inorganic PTC compound, no greater than about5% by weight of the crosslinked polymer, no greater than about 2% byweight of the conductive material, and no greater than about 10% byweight of the filler.

In one embodiment, the PTC film comprises barium titanate, a crosslinkedpolyamide-imide, carbon black, and CMC and/or SBR. In anotherembodiment, the PTC film comprises no less than about 50% by weight ofbarium titanate, no greater than about 50% by weight of the crosslinkedpolyamide-imide, no greater than about 5% by weight of carbon black, andno greater than about 30% by weight of CMC and SBR. In yet anotherembodiment, the PTC film comprises no less than about 60% by weight ofbarium titanate, no greater than about 40% by weight of the crosslinkedpolyamide-imide, no greater than about 5% by weight of carbon black, andno greater than about 10% by weight of CMC and SBR. In yet anotherembodiment, the PTC film comprises no less than about 70% by weight ofbarium titanate, no greater than about 30% by weight of the crosslinkedpolyamide-imide, no greater than about 5% by weight of carbon black, andno greater than about 10% by weight of CMC and SBR. In yet anotherembodiment, the PTC film comprises no less than about 75% by weight ofbarium titanate, no greater than about 25% by weight of the crosslinkedpolyamide-imide, no greater than about 5% by weight of carbon black, andno greater than about 10% by weight of CMC and SBR. In yet anotherembodiment, the PTC film comprises no less than about 80% by weight ofbarium titanate, no greater than about 20% by weight of the crosslinkedpolyamide-imide, no greater than about 2% by weight of carbon black, andno greater than about 10% by weight of CMC and SBR. In still anotherembodiment, the PTC film comprises no less than about 85% by weight ofbarium titanate, no greater than about 15% by weight of the crosslinkedpolyamide-imide, no greater than about 2% by weight of carbon black, andno greater than about 10% by weight of CMC and SBR.

In one embodiment, the PTC film comprises barium titanate, a crosslinkedpolypropylene, carbon black, and CMC or SBR. In another embodiment, thePTC film comprises no less than about 50% by weight of barium titanate,no greater than about 50% by weight of the crosslinked polypropylene, nogreater than about 5% by weight of carbon black, and no greater thanabout 30% by weight of CMC and SBR. In yet another embodiment, the PTCfilm comprises no less than about 60% by weight of barium titanate, nogreater than about 40% by weight of the crosslinked polypropylene, nogreater than about 5% by weight of carbon black, and no greater thanabout 10% by weight of CMC and SBR. In yet another embodiment, the PTCfilm comprises no less than about 70% by weight of barium titanate, nogreater than about 30% by weight of the crosslinked polypropylene, nogreater than about 5% by weight of carbon black, and no greater thanabout 10% by weight of CMC and SBR. In yet another embodiment, the PTCfilm comprises no less than about 75% by weight of barium titanate, nogreater than about 25% by weight of the crosslinked polypropylene, nogreater than about 5% by weight of carbon black, and no greater thanabout 10% by weight of CMC and SBR. In yet another embodiment, the PTCfilm comprises no less than about 80% by weight of barium titanate, nogreater than about 20% by weight of the crosslinked polypropylene, nogreater than about 2% by weight of carbon black, and no greater thanabout 10% by weight of CMC and SBR. In still another embodiment, the PTCfilm comprises no less than about 85% by weight of barium titanate, nogreater than about 15% by weight of the crosslinked polypropylene, nogreater than about 2% by weight of carbon black, and no greater thanabout 10% by weight of CMC and SBR.

In another embodiment, provided herein is a PTC film comprising no lessthan about 70% by weight of an inorganic PTC compound, in oneembodiment, particles of the inorganic PTC compound, and no greater thanabout 30% by weight of one or more polymers. In one embodiment, the PTCfilm provided herein comprises no less than about 75% by weight of aninorganic PTC compound and no greater than about 25% by weight of one ormore polymers. In another embodiment, the PTC film provided hereincomprises no less than about 80% by weight of an inorganic PTC compoundand no greater than about 20% by weight of one or more polymers. In yetanother embodiment, the PTC film provided herein comprises no less thanabout 85% by weight of an inorganic PTC compound and no greater thanabout 15% by weight of one or more polymers. In yet another embodiment,the PTC film provided herein comprises no less than about 90% by weightof an inorganic PTC compound and no greater than about 10% by weight ofone or more polymers. In still another embodiment, the PTC film providedherein comprises no less than about 95% by weight of an inorganic PTCcompound and no greater than about 5% by weight of one or more polymers.

In certain embodiments, the polymer is a polybenzophenone, polyacrylate,polyvinyl, polypropylene, polystyrene, polysulfone,2,3-dihydrofuran-containing polymer, CMC, polyamide-imide, polyimide,styrene-containing copolymer, PTFE, PVDF, PVA, SBR, polyethylene,polypropylene, or a combination thereof.

In certain embodiments, the polymer is a polybenzophenone, polyacrylate,polyvinyl, polypropylene, polystyrene, polysulfone,2,3-dihydrofuran-containing polymer, CMC, polyamide-imide, polyimide,styrene-containing copolymer, PTFE, PVDF, PVA, SBR, or a combinationthereof.

In certain embodiments, the polymer is a PTC polymer. In certainembodiments, the PTC polymer is a polyethylene or polypropylene. Incertain embodiments, the PTC polymer is high-density polyethylene or lowdensity polyethylene. In certain embodiments, the PTC polymer ishigh-density polypropylene or low density polypropylene.

In certain embodiments, the polymer is a crosslinked polymer. In certainembodiments, the crosslinked polymer is a crosslinkable polymer.

In one embodiment, the PTC film provided herein comprises no less thanabout 70% by weight of barium titanate and no greater than about 30% byweight of PVDF, polyamide-imide, polypropylene, SBR, CMC, or a mixturethereof. In another embodiment, the PTC film provided herein comprisesno less than about 75% by weight of barium titanate and no greater than25% by weight of PVDF, polyamide-imide, polypropylene, SBR, CMC, or amixture thereof. In yet another embodiment, the PTC film provided hereincomprises no less than about 80% by weight of barium titanate and nogreater than 20% by weight of PVDF, polyamide-imide, polypropylene, SBR,CMC, or a mixture thereof. In yet another embodiment, the PTC filmprovided herein comprises no less than about 85% by weight of bariumtitanate and no greater than 15% by weight of PVDF, polyamide-imide,polypropylene, SBR, CMC, or a mixture thereof. In yet anotherembodiment, the PTC film provided herein comprises no less than about90% by weight of barium titanate and no greater than 10% by weight ofPVDF, polyamide-imide, polypropylene, SBR, CMC, or a mixture thereof. Instill another embodiment, the PTC film provided herein comprises no lessthan about 95% by weight of barium titanate and no greater than 5% byweight of PVDF, polyamide-imide, polypropylene, SBR, CMC, or a mixturethereof.

In certain embodiments, the PTC film provided herein further comprises aconductive material as described herein. Thus, in one embodiment,provided herein is a PTC film comprising (i) no less than about 70% byweight of an inorganic PTC compound, in one embodiment, particles of theinorganic PTC compound; (ii) no greater than about 30% by weight of oneor more polymers; and (iii) no greater than about 5% by weight of aconductive material, in one embodiment, particles of the conductivematerial. In another embodiment, the PTC film provided herein comprisesno less than about 75% by weight of an inorganic PTC compound, nogreater than about 25% by weight of one or more polymers, and no greaterthan about 5% by weight of a conductive material. In yet anotherembodiment, the PTC film provided herein comprises no less than about80% by weight of an inorganic PTC compound, no greater than about 20% byweight of one or more polymers, and no greater than about 5% by weightof a conductive material. In yet another embodiment, the PTC filmprovided herein comprises no less than about 85% by weight of aninorganic PTC compound, no greater than about 15% by weight of one ormore polymers, and no greater than about 5% by weight of a conductivematerial. In yet another embodiment, the PTC film provided hereincomprises no less than about 90% by weight of an inorganic PTC compound,no greater than about 10% by weight of one or more polymers, and nogreater than about 5% by weight of a conductive material. In stillanother embodiment, the PTC film provided herein comprises no less thanabout 95% by weight of an inorganic PTC compound, no greater than 5% byweight of one or more polymers, and no greater than about 5% by weightof a conductive material.

In yet another embodiment, provided herein is a PTC film comprising aninorganic PTC compound, one or more polymers, and optionally aconductive material; wherein the PTC film is formed using a mixture ofthe inorganic PTC compound, the polymer(s), and optionally theconductive material in water as a solvent.

In yet another embodiment, provided herein is a method for preparing aPTC film that comprises an inorganic PTC compound, a crosslinkedpolymer, optionally a conductive material, and optionally a filler;comprising the steps of:

(i) coating a mixture, in one embodiment, a slurry, of the inorganic PTCcompound, the crosslinked polymer, optionally the conductive material,and optionally the filler in a solvent onto at a flat surface to form awet PTC film; and

(ii) curing the crosslinking the wet PTC film to form the PTC film.

In yet another embodiment, provided herein is a method for preparing aPTC film that comprises an inorganic PTC compound, a crosslinkedpolymer, optionally a conductive material, and optionally a filler;comprising the steps of:

(i) coating a mixture, in one embodiment, a slurry, of the inorganic PTCcompound, a precursor of the crosslinked polymer, in one embodiment, acrosslinkable polymer, optionally the conductive material, andoptionally the filler in a solvent onto at a flat surface to form a wetPTC film; and

(ii) curing the wet PTC film to crosslink the precursor to form thecrosslinked polymer and thus to form the PTC film.

In certain embodiments, the solvent is a polar solvent. In certainembodiments, the solvent is an organic solvent. In certain embodiments,the solvent is a polar organic solvent. In certain embodiments, thesolvent is an amide. In certain embodiments, the solvent isN-methylpyrrolidone (NMP). In certain embodiments, the solvent is water.

In certain embodiments, the flat surface is a surface of a metal film orfoil. In certain embodiments, the flat surface is a surface of a currentcollector.

In certain embodiments, the mixture of the inorganic PTC compound and aprecursor of the crosslinked polymer is a slurry or paste of particlesof the inorganic PTC compound. In certain embodiments, the precursor ofthe crosslinked polymer is dissolved in the solvent.

In certain embodiments, the crosslinking step is performed by curing themixture of the precursor and the inorganic PTC compound at an elevatedtemperature. In certain embodiments, the elevated temperature is rangingfrom about 100 to about 1,000° C., from about 150 to about 750° C., fromabout 200 to about 700° C., from about 300 to about 600° C., or fromabout 300 to about 500° C. In certain embodiments, the elevatedtemperature is about 200, about 250, about 300, about 350, about 400,about 450, about 500, about 550, or about 600° C.

In certain embodiments, the crosslinking step is performed by curing themixture of the precursor and the inorganic PTC compound by removing thesolvent, e.g., evaporation.

In still another embodiment, provided herein is a method for preparing aPTC film comprising an inorganic PTC compound, one or more polymers, andoptionally a conductive material; wherein the method comprises the stepsof:

(i) coating a mixture of the inorganic PTC compound, the polymer(s), andoptionally the conductive material in water onto at a flat surface toform a wet PTC film; and

(ii) curing, in one embodiment, drying, the wet film to form the PTCfilm.

In certain embodiments, the method provided herein further comprises thestep of pressing the PTC film to reduce the thickness of the PTC film.

Positive Temperature Coefficient Electrodes

In one embodiment, provided herein is a PTC electrode comprising (i) acurrent collector having a surface; and (ii) one or more PTC films; and(iii) one or more electroactive material layers; wherein the PTCelectrode has the same number of the PTC films as the electroactivematerial layers; wherein the PTC films are disposed as such that no twoPTC films are in direct contact; and wherein one PTC film is disposed assuch that the PTC film is in direct contact with the surface of thecurrent collector, or one electroactive material layer is disposed assuch that the electroactive material layer is in direct contact with thesurface of the current collector. In one embodiment, one of the PTCfilms is in direct contact with the surface of the current collector. Inanother embodiment, one of the electroactive material layers is indirect contact with the surface of the current collector.

In one embodiment, provided herein is a PTC electrode comprising (i) acurrent collector; (ii) a PTC film; and (iii) an electroactive materiallayer.

In another embodiment, provided herein is a PTC electrode comprising (i)a current collector; (ii) a PTC film comprising an inorganic PTCcompound, a polymer, and optionally a conductive material; and (ii) anelectroactive material layer; wherein the PTC film is formed using afirst solvent and the electroactive material layer is formed using asecond solvent.

In certain embodiments, the first solvent is water. In certainembodiments, the second solvent is an organic solvent. In certainembodiments, the second solvent is an amide. In certain embodiments, thesecond solvent is NMP.

In yet another embodiment, provided herein is a PTC electrode comprising(i) a current collector; (ii) a ceramic PTC film comprising an inorganicPTC compound; and (iii) an electroactive material layer.

In certain embodiments, the PTC film is disposed between the currentcollector and the electroactive material layer. In certain embodiments,the electroactive material layer is disposed between the currentcollector and the PTC film.

In another embodiment, provided herein is a PTC electrode comprising (i)a current collector with a surface; and (ii) one or more PTC films; and(iii) one or more electroactive material layers; wherein the PTCelectrode has one PTC film more than the number of the electroactivematerial layers on the surface of the current collector; wherein the PTCfilms are disposed as such that no two PTC films are in direct contactand each electroactive material layer is sandwitched between two PCTfilms; and wherein one PTC film is disposed as such that the PTC film isin direct contact with the surface of the current collector.

In still another embodiment, provided herein is a PTC electrodecomprising (i) a current collector having a first and second surface;(ii) one or more positive temperature coefficient films on the firstsurface of the current collector and one or more positive temperaturecoefficient films on the second surface of the current collector; and(iii) one or more electroactive material layers on the first surface ofthe current collector and one or more electroactive material layers onthe second surface of the current collector; wherein the electrode hasthe same number of the PTC films as the electroactive material layers onthe first surface of the current collector; wherein the electrode hasthe same number of the PTC films as the electroactive material layers onthe second surface of the current collector; wherein the electroactivefilms on each surface of the current collector are disposed as such thatno two PTC films are in direct contact.

In one embodiment, one of the PTC films is in direct contact with thefirst surface of the current collector. In another embodiment, one ofthe electroactive material layers is in direct contact with the firstsurface of the current collector. In yet another embodiment, one of thePTC films is in direct contact with the second surface of the currentcollector. In still another embodiment, one of the electroactivematerial layers is in direct contact with the second surface of thecurrent collector.

In certain embodiments, the PTC electrode has the same number of the PTCfilms on the first surface of the current collector as the PTC films onthe second surface of the current collector.

In certain embodiments, the PTC electrode is a PTC anode. In certainembodiments, the PTC electrode is a PTC cathode.

In certain embodiments, the current collector is a metal. In certainembodiments, the current collector is aluminum, copper, nickel, silver,or a combination thereof. In certain embodiments, the current collectoris a metal foil. In certain embodiments, the current collector isaluminum foil, copper foil, nickel foil, or silver foil, or acombination thereof.

In certain embodiments, the current collector for the anode is copper.In certain embodiments, the current collector for the anode is copperfoil. In certain embodiments, the current collector for the anode isrolled copper foil. In certain embodiments, the current collector forthe anode is electrodeposited copper foil.

In certain embodiments, the current collector for the cathode isaluminum, nickel, silver, or a combination thereof. In certainembodiments, the current collector for the cathode is aluminum foil,nickel foil, silver foil, graphite foil (e.g., GRAFOIL®), or acombination thereof. In certain embodiments, the current collector forthe cathode is aluminum foil. In certain embodiments, the currentcollector for the cathode is nickel foil. In certain embodiments, thecurrent collector for the cathode is silver foil.

In certain embodiments, the electroactive material layer comprises anelectroactive material and a binder. In certain embodiments, the binderis PVDF, CMC, SBR, a polyamide-imide, a polyimide, ethylene propylenediene monomer (EPDM), a polyethylene oxide (PEO or PEG), apolyethersulfone, a polyphenylsulfone, or a mixture thereof.

The electroactive material for the anode can be any electroactivematerial known to one of ordinary skill in the art.

In certain embodiments, the electroactive material for an anode is anelectroactive metal or metal oxide. Suitable electroactive metals andmetal oxides include, but are not limited to, silicon (Si), siliconmonoxide (SiO), Si₂N₂O, Ge₂N₂O, boron oxide, titanium oxides (includingtitanium monoxide, titanium(III) oxide, and titanium dioxide), tin, tinoxides (including tin(II) oxide (SnO) and tin dioxide (SnO₂)), antimony,magnesium, zinc, zirconium oxide, cadmium, indium, aluminum, bismuth,germanium, lead, vanadium oxide, cobalt oxide, WO₂, and combinationsthereof. In certain embodiments, the electroactive material for an anodeis Li₄Ti₅O₁₂, Si₇₀Fe₁₀Ti₁₀C₁₀, TiS₂, MoS₂, or a combination thereof. Incertain embodiments, the electroactive material for an anode is Si, SiO,Li₄Ti₅O₁₂, SnO, WO₂, Si₇₀Fe₁₀Ti₁₀C₁₀, TiS₂, MoS₂, WS₂, or a mixturethereof.

In certain embodiments, the electroactive material for an anode is anelectroactive alloy. Suitable electrochemically active alloys include,but are not limited to, silicon alloys containing tin, a transitionmetal, and/or optionally carbon; silicon alloys containing a transitionmetal and/or aluminum; silicon alloys containing copper and/or silver;and alloys containing tin, silicon, aluminum, yttrium, a lanthanide, anactinide, or a combination thereof. In certain embodiments, theelectrochemically active alloy is SnSb, SnAg, AgSi, GaSb, AlSb, InSb,Sb₂Ti, Sb₂V, Sn₂Sn, Cu₂Sb, Cr₂Sb, or a mixture thereof. In certainembodiments, the electrochemically active alloy is a multiple phasealloy, including, but not limited to, Sn/SnSb_(x), Sn/SnAg_(x),SnF/SnFeC, and SnMnC, wherein each x is independently greater than 0 butsmaller than about 10, in one embodiment, about 0.1, about 0.2, about0.5, about 1, about 2, about 3, about 4, about 5, about 6, about 7,about 8, about 9, or about 10. In certain embodiments, SnSb isSnSb_(0.39). In certain embodiments, SnAg is SnAg_(0.1), SnAg_(0.32),SnAg_(0.39), SnAg₃, or SnAg₄. In certain embodiments, the electroactivematerial for an anode is silicon. In certain embodiments, the silicon isdoped with boron, aluminum, gallium, antimony, phosphorus, or acombination thereof. In certain embodiments, the electroactive materialfor an anode comprises silicon, in one embodiment, silicon powder, andcarbon. In certain embodiments, the electroactive material for an anodeis a mixture of silicon, in one embodiment, silicon powder, and carbon.

In certain embodiments, the electroactive material for the anode iscarbon. In certain embodiments, the electroactive material for the anodeis a carbonaceous material. In certain embodiments, the electroactivematerial for the anode is mesocarbon microbead. In certain embodiments,the carbonaceous material for the anode is graphene, graphite, coke,petroleum coke, carbon, a partially or fully graphitized carbon,carbon-black, hard carbon, or a mixture thereof.

In certain embodiments, the electroactive material for the anode is acoated electroactive particle. In certain embodiments, the electroactivematerial for the anode is coated silicon particle. In certainembodiments, the electroactive material for the anode is a siliconparticle coated with a polymer. In certain embodiments, theelectroactive material for the anode is a silicon particle coated with acrosslinked polymer.

In certain embodiments, the electroactive material for the anode is asilicon particle coated with a crosslinked polyamide-imide. In certainembodiments, the electroactive material for the anode is a siliconparticle coated with a crosslinked polyimide. In certain embodiments,the electroactive material for the anode is a silicon particle coatedwith crosslinked CMC. In certain embodiments, the electroactive materialfor the anode is a silicon particle coated with crosslinked polysulfone.

The electroactive material for the cathode can be any electroactivematerial known to one of ordinary skill in the art.

In certain embodiments, the electroactive material for a cathode is alithium compound. In one embodiment, the electroactive material for acathode is a lithium phosphate compound. In another embodiment, theelectroactive material for a cathode is LiMPO₄, wherein M is atransition metal. In certain embodiments, M is a transition metalselected from the group consisting of Ti, V, Cr, Mn, Fe, Co, and Ni. Inyet another embodiment, the electroactive material for a cathode isLiFePO₄. In yet another embodiment, the electroactive material for acathode is LiMnPO₄. In yet another embodiment, the electroactivematerial for a cathode is LiVPO₄. In yet another embodiment, theelectroactive material for a cathode is AM^(a) _(1-d)M^(b) _(d)PO₄,wherein A is Li, Na, or a mixture thereof; M^(a) is Fe, Co, Mn, or amixture thereof, M^(b) is Mg, Ca, Zn, Ni, Co, Cu, Al, B, Cr, Nb, or amixture thereof and d is ranging from about 0.01 to about 0.99, fromabout 0.01 to about 0.5, from about 0.01 to about 0.30, or from about0.01 to about 0.15. In yet another embodiment, the electroactivematerial for a cathode is LiM^(a) _(1-d)M^(b) _(d)PO₄, wherein M^(a),M^(b), and d are each as defined herein. In still another embodiment,the electroactive material for a cathode is NaM^(a) _(1-d)M^(b) _(d)PO₄,wherein M^(a), M^(b), and d are each as defined herein.

In certain embodiments, the electroactive material for a cathode is(LiF)_(x)Fe_(1-x), wherein 0<x<1.

In certain embodiments, the electroactive material for a cathode is ametal oxide. In one embodiment, the electroactive material for a cathodeis selected from the group consisting of LiMn₂O₄, LiCoO₂, LiNiCoO₂,LiNicCo_(1-c)O₂, where c is from about 0.05 to about 0.95, from about0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 toabout 0.4, Li(NiMnCo)_(1/3)O₂, Li(NiMn)_(1/2)O₂, LiV₂O₅, LiAlNiCoO₂,LiNi_(1-a-b)Al_(a)Co_(b)O₂, where a is from about 0.01 to about 0.5 andb is from about 0.01 to about 0.9, with the proviso that the sum of aand b is less than 1; and c is from about 0.01 to about 0.99, andmixtures thereof. In one embodiment, the electroactive material isLiMn₂O₄. In another embodiment, the electroactive material for a cathodeis LiCoO₂. In yet another embodiment, the electroactive material for acathode is LiNiCoO₂. In yet another embodiment, the electroactivematerial for a cathode is LiNicCo_(1-c)O₂, wherein c is from about 0.2to about 0.5, from about 0.2 to about 0.4, or about 0.3. In yet anotherembodiment, the electroactive material for a cathode isLi(NiMnCo)_(1/3)O₂. In yet another embodiment, the electroactivematerial for a cathode is Li(NiMn)_(1/2)O₂. In yet another embodiment,the electroactive material for a cathode is LiV₂O₅. In still anotherembodiment, the electroactive material for a cathode is LiAlNiCoO₂.

In yet another embodiment, the electroactive material for a cathode isLiNi_(e)Mn_(f)Co_(1-e-f)O₂, wherein e and f are each independentlyranging from 0 to about 0.95, from about 0.01 to about 0.9, from about0.05 to about 0.80, from about 0.1 to about 0.5, or from about 0.2 toabout 0.4, and the sum of e and f is less than 1. In yet anotherembodiment, the electroactive material for a cathode isLiNi_(e)Mn_(f)Co_(1-e-f)O₂, wherein e and f are 0.33.

In still another embodiment, the electroactive material for a cathode isLiNi_(1-a-b)Al_(a)Co_(b)O₂, wherein a is from about 0.01 to about 0.9,from about 0.01 to about 0.7, from about 0.01 to about 0.5, from about0.01 to about 0.4, from about 0.01 to about 0.3, from about 0.01 toabout 0.2, or from about 0.01 to about 0.1; and b is from about 0.01 toabout 0.9, from about 0.01 to about 0.7, from about 0.01 to about 0.5,from about 0.01 to about 0.4, from about 0.01 to about 0.3, from about0.01 to about 0.2, or from about 0.01 to about 0.1; with the provisothat the sum of a and b is less than 1. In certain embodiments, a isfrom about 0.01 to about 0.5. In certain embodiments, a is from about0.01 to about 0.1. In certain embodiments, b is from about 0.01 to about0.9. In certain embodiments, b is from about 0.01 to about 0.2. Incertain embodiments, a is from about 0.01 to about 0.1 and b is fromabout 0.01 to about 0.2. In certain embodiments, the electroactivematerial for a cathode is LiAl_(0.05)Ni_(0.8)Co_(0.15)O₂. In certainembodiments, the electroactive material for a cathode is Li₂FeSiO₄,Li₂MnSiO₄, or a mixture thereof. In certain embodiments, theelectroactive material for a cathode is Li₂FeSiO₄. In certainembodiments, the electroactive material for a cathode is Li₂MnSiO₄.

In certain embodiments, the electroactive material for the cathode iselectroactive agglomerated particles. Examples of suitable electroactiveagglomerated particles include those as described in U.S. Pat. App. Pub.No. 2008/0116423, the disclosure of which is incorporated herein byreference in its entirety.

In one embodiment, provided herein is a method for preparing a PTCelectrode that comprises (a) a current collector having a surface; (b) aPTC film comprising an inorganic PTC compound, a crosslinked polymer,optionally a conductive material, and optionally a filler; and (c) anelectroactive material layer; comprising the steps of:

(i) coating a mixture of the inorganic PTC compound, the crosslinkedpolymer, optionally the conductive material, and optionally the fillerin a first solvent onto the surface of the current collector to form aweb PTC film;

(ii) curing the wet PTC film to form the PTC film; and

(iii) coating a mixture of the electroactive material in a secondsolvent onto the surface of the PTC film to form the electroactivematerial layer and thus to form the PTC electrode.

In another embodiment, provided herein is a method for preparing a PTCelectrode that comprises (a) a current collector having a surface; (b) aPTC film comprising an inorganic PTC compound, a crosslinked polymer,optionally a conductive material, and optionally a filler; and (c) anelectroactive material layer; comprising the steps of:

(i) coating a mixture of the inorganic PTC compound, a precursor of thecrosslinked polymer, in one embodiment, a crosslinkable polymer,optionally the conductive material, and optionally the filler, in afirst solvent onto the surface of the current collector to form a wetPTC film;

(ii) curing the wet PTC film by crosslinking the precursor to form thecrosslinked polymer and thus to form the PTC film; and

(iii) coating a mixture of the electroactive material in a secondsolvent onto the surface of the PTC film to form the electroactivematerial layer and thus to form the PTC electrode.

In yet another embodiment, provided herein is a method for preparing aPTC electrode that comprises (a) a current collector having a surface;(b) a PTC film comprising an inorganic PTC compound, a polymer, andoptionally a conductive material; and (c) an electroactive materiallayer; comprising the steps of:

(i) coating a mixture of the inorganic PTC compound, the polymer, andoptionally the conductive material in a first solvent onto at thesurface of the current collector to form the PTC film; and

(ii) coating a mixture of the electroactive material in a second solventonto the surface of the PTC film to form the electroactive materiallayer and thus to form the PTC electrode.

In certain embodiments, the first solvent is water. In certainembodiments, the second solvent is an organic solvent. In certainembodiments, the second solvent is an amide. In certain embodiments, thesecond solvent is NMP.

Positive Temperature Coefficient Separators

In one embodiment, provided herein is a PTC separator with a surface,comprising a separator and a PTC film, wherein the PTC film is in directcontact with the surface of the separator.

In another embodiment, provided herein is a PTC separator with a firstand second surface, comprising a separator and two PTC films, whereinone PTC film is in direct contact with the first surface of theseparator and the other PTC film is in direct contact with the secondsurface of the separator.

The separator can be any separator known to one of ordinary skill in theart.

In one embodiment, the separator is a plastic film. In certainembodiments, the separator is porous plastic film. In certainembodiments, the separator is microporous. In another embodiment, theseparator is a polyolefin. In yet another embodiment, the separator is apolyethylene film, a polypropylene film, or a combination thereof.

Lithium Secondary Battery

In one embodiment, provided herein is a lithium secondary battery, whichcomprises (i) an anode; (ii) a cathode; (iii) a separator that separatesthe anode and cathode; and (iv) electrolyte; wherein at least one of theanode, cathode, and separator contains a PTC film provided herein.

In another embodiment, provided herein is a lithium secondary battery,which comprises (i) an anode; (ii) a cathode; (iii) a separator thatseparates the anode and cathode; and (iv) electrolyte; wherein at leastone of the anode and cathode is a PTC electrode.

In another embodiment, the lithium secondary battery provided hereincomprises (i) a PTC anode; (ii) a cathode; (iii) a separator thatseparates the anode and cathode; and (iv) electrolyte.

In yet another embodiment, the lithium secondary battery provided hereincomprises (i) an anode; (ii) a PTC cathode; (iii) a separator thatseparates the anode and cathode; and (iv) electrolyte.

In yet another embodiment, the lithium secondary battery provided hereincomprises (i) an anode; (ii) a cathode; (iii) a PTC separator thatseparates the anode and cathode; and (iv) electrolyte.

In still another embodiment, the lithium secondary battery providedherein comprises (i) a PTC anode; (ii) a PTC cathode; (iii) a PTCseparator that separates the anode and cathode; and (iv) electrolyte.

The non-PTC anode, non-PTC cathode, and non-PTC separator can be anyanode, cathode, separator known to one of ordinary skill in the art.

Any electrolytes known to one of ordinary skill in the art can be usedin the batteries provided herein.

In certain embodiments, the electrolyte comprises one or more lithiumsalts and a charge carrying medium in the form of a solid, liquid, orgel. Suitable lithium salts include, but are not limited to LiPF₆,LiBF₄, LiClO₄, lithium bis(oxalato)borate, LiN(CF₃SO₂)₂, LiN(C₂F₅SO₂)₂,LiAsF₆, LiC(CF₃SO₂)₃, and combinations thereof.

Suitable examples of solid charge carrying media include, but are notlimited to, polymeric media, e.g., polyethylene oxide. Suitable examplesof liquid charge carrying media include, but are not limited to,ethylene carbonate, propylene carbonate, dimethyl carbonate, diethylcarbonate, ethyl-methyl carbonate, butylene carbonate, vinylenecarbonate, fluorinated ethylene carbonate, fluorinated propylenecarbonate, γ-butylrolactone, methyl difluoroacetate, ethyldifluoroacetate, dimethoxyethane, diglyme (i.e., bis(2-methoxyethyl)ether), tetrahydrofuran, dioxolane, and combinations thereof. Suitableexamples of charge carrying media gels include those described in U.S.Pat. Nos. 6,387,570 and 6,780,544, the disclosure of each of which isincorporated herein by reference in its entirety.

The disclosure will be further understood by the following non-limitingexamples.

EXAMPLES Example 1 General Procedure for PTC Electrode Fabrication

To a solution of a polymer (e.g., TORLON®-4000 (polyamide-imide), BM700,or CMC) and/or a filler (e.g., PVDF, SBR, sodium naphthalene sulfonate)in NMP were added barium titanate and optionally carbon black to form aslurry or paste. The slurry or paste was coated onto a surface of analuminum foil to form a wet barium titanate-containing layer. The wetbarium titanate-containing layer was dried to form a PTC layer.

To a solution of a binder (e.g., PVDF) in NMP were added conductivecarbon black and LiNiCoAlO₂ (NCA) to form a slurry. The slurry wascoated onto the surface of the PTC layer to form a wet electroactivematerial layer. The wet electroactive material layer was compressed tothe designed thickness. The positive PTC electrode was dried at 125° C.for 10 hours.

Example 2 General Procedure for PTC Electrode Fabrication

To a solution of a binder (e.g., PVDF) in NMP were added conductivecarbon black and LiNiCoAlO₂ (NCA) to form a slurry. The slurry wascoated onto an electrode surface. The wet electroactive material layerwas compressed to the designed thickness. The electrode was dried at125° C. for 10 hours.

To a solution of a polymer (e.g., TORLON®-4000 (polyamide-imide), BM700,or CMC) and/or a filler (e.g., PVDF, SBR, sodium naphthalene sulfonate)in NMP were added barium titanate and optionally carbon black to form aslurry or paste. The slurry or paste was coated onto the electrodesurface to form a wet barium titanate-containing layer. The wet bariumtitanate-containing layer was dried to form a PTC layer and thus a PTCelectrode.

Example 3 Cell Fabrication

A non-PTC negative electrode comprising polyamide-imide coated Sinanoparticles was coated onto a Cu foil using a small doctor bladecoater, and then calendared to the designed thickness. The negativeelectrode was then drive at 140° C. for 10 hours. Once the positive andnegative electrodes were dried, all subsequent cell fabrication stepswere carried out inside a drying room at a Dew point of about −35° C.The electrodes were tabbed first and then wound into a jellyroll orlaminated into a jellyflate. The jellyroll was then inserted into abattery can, such as an 18650 can and a 4 mm thick pouch cell. Thejellyroll was then dried at 75° C. for 10 hours. An electrolyte was putinto the cell under vacuum. The cell was crimped for sealing a 18650cell or thermally sealed for a 4 mm thick poun cell after electrolytefilling.

Example 4 Nail Test

The cell was charged at 2 A to 4.2V for 3 hours. The cell was placed ona surface of a flat metal. A thermal couple was attached to the surfaceof the cell to follow the temperature of the cell during the test. Thepositive and negative tabs were connected to a voltage and resistancemeter. A nail was shot at the cell at the speed of 1 mm/sec. The nailcompletely penetrated the cell. The nail was left inside the cell untilthe cell temperature returned to room temperature.

Example 5 Overcharge Test

The cell was charged at 2 A to 4.2V for 3 hours. The cell was placed ina chamber. A thermal couple was attached to the surface of the cell tofollow the temperature of the cell during the test. The positive andnegative tabs were connected to a voltage and resistance meter. The cellwas overcharged with a power supplier until the cell temperature wasclose to room temperature.

Example 6 Thermal Spraying

To a solution of a polymer (e.g., TORLON®-4000 (polyamide-imide), BM700,or CMC) and/or a filler (e.g., PVDF, SBR, sodium naphthalene sulfonate)in NMP were added barium titanate and optionally carbon black to form aPTC slurry or paste.

To a solution of a binder (e.g., PVDF) in NMP were added conductivecarbon black and LiNiCoAlO₂ (NCA) to form an electrode active materialslurry.

First, the PTC slurry was thermally sprayed onto the surface of acurrent collector as a PTC film. Then, the electrode active materialslurry was coated onto the surface of the PTC film. The electrode withthe PTC layer then was wound into either jellyroll or jellyflat to bemade into a cell.

Example 7 PTC Films

Compositions of four PTC films are summarized in Table 1. Samples 1 to 3were prepared using NMP as a solvent, according to the procedure asdescribed in Example 1. Sample 4 was prepared using water as a solvent,according to the procedure as described in Example 1. Samples 5 to 7were prepared for comparison, according to the procedure as described inExample 1

Each of the samples was tested as a part of a cathode for a lithiumsecondary battery as described in Example 3. The test results aresummarized in Table 3.

TABLE 1 PTC Films Sample No. Components Loading (mg/cm²) 1 Carbon black 1% 2 TORLON ®-4000  29% (Polyamide-imide) Barium titanate  70% 2 Carbonblack  1% 0.5 PVDF 7.5% Barium titanate  84% BM700 (A polypropylene)7.5% 3 PVDF 7.5% 2 Barium titanate  85% BM700 (Polypropylene) 7.5% 4Carbon black  1% 0.7 SBR 8.5% Barium titanate 84.5%  CMC  3% Sodiumnaphthalene  3% sulfonate

TABLE 2 Comparative Films Sample No. Components Loading (mg/cm²) 5Carbon black 10% 0.25 PVDF 90% 6 Carbon black 10% 0.25 TORLON ®-4000 10%(Polyamide-imide) PVDF 80% 7 Carbon black  1% 2 PVDF 29% Barium titanate84%

TABLE 3 Test Results Sample No. Nail Test Overcharge Test 1 Pass Pass 2Pass 3 Pass 4 Pass 5 Fail 6 Pass Fail 7 Pass Fail

The examples set forth above are provided to give those of ordinaryskill in the art with a complete disclosure and description of how tomake and use the claimed embodiments, and are not intended to limit thescope of what is disclosed herein. Modifications that are obvious topersons of skill in the art are intended to be within the scope of thefollowing claims. All publications, patents, and patent applicationscited in this specification are incorporated herein by reference as ifeach such publication, patent or patent application were specificallyand individually indicated to be incorporated herein by reference.

1.-28. (canceled)
 29. A battery electrode, comprising: a firstelectroactive layer comprising an electroactive material; and a firstpositive temperature coefficient (PTC) film disposed on one side of theelectroactive layer, the first PTC film comprising barium titanate and acrosslinked polymer.
 30. The battery electrode of claim 29, wherein thebarium titanate is in the form of nanoparticles.
 31. The batteryelectrode of claim 29, wherein the crosslinked polymer is formed in thepresence of barium titanate.
 32. The battery electrode of claim 29,wherein the crosslinked polymer comprises a crosslinkedpolybenzophenone, a crosslinked polyacrylate, a crosslinked polyvinyl, acrosslinked polyethylene, a crosslinked polypropylene, a crosslinkedpolystyrene, a crosslinked polysulfone, a crosslinked2,3-dihydrofuran-containing polymer, a crosslinked carboxymethylcellulose (CMC), a crosslinked polyamide-imide, a crosslinked polyimide,and/or a crosslinked styrene-containing copolymer.
 33. The batteryelectrode of claim 29, wherein the crosslinked polymer comprises athermally crosslinked polymer.
 34. The battery electrode of claim 29,wherein the first PTC film comprises no less than about 50% by weight ofbarium titanate and no greater than about 50% by weight of thecrosslinked polymer.
 35. The battery electrode of claim 34, wherein thefirst PTC film comprises no less than about 70% by weight of bariumtitanate and no greater than about 30% by weight of the crosslinkedpolymer.
 36. The battery electrode of claim 29, wherein the first PTCfilm further comprises a conductive material.
 37. The battery electrodeof claim 36, wherein the conductive material comprises carbon black. 38.The battery electrode of claim 36, wherein the first PTC film comprisesno less than about 50% by weight of barium titanate, no greater thanabout 50% by weight of the crosslinked polymer, and no greater thanabout 5% by weight of the conductive material.
 39. The battery electrodeof claim 38, wherein the first PTC film comprises no less than about 70%by weight of barium titanate, no greater than about 30% by weight of thecrosslinked polymer, and no greater than about 2% by weight of theconductive material.
 40. The battery electrode of claim 29, wherein thefirst PTC film further comprises a filler.
 41. The battery electrode ofclaim 40, wherein the filler comprises a polymer.
 42. The batteryelectrode of claim 40, wherein the filler comprises asphalt pitch, pitchcoke, petroleum coke, a sugar, coal tar, fluoranthene, pyrene, chrysene,phenanthrene, anthracene, naphthalin, fluorene, biphenyl, acenephthene,a solid ionic conductor, a polyamide-imide, a polyimide,polytetrafluoroethylene (PTFE), a crosslinked carboxymethyl cellulose(CMC), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), and/orstyrene butadiene rubber (SBR).
 43. The battery electrode of claim 40,wherein the first PTC film comprises no less than about 50% by weight ofbarium titanate, no greater than about 50% by weight of the crosslinkedpolymer, no greater than about 5% by weight of the conductive material,and no greater than about 10% by weight of the filler.
 44. The batteryelectrode of claim 40, wherein the first PTC film comprises no less thanabout 70% by weight of barium titanate, no greater than about 30% byweight of the crosslinked polymer, no greater than about 2% by weight ofthe conductive material, and no greater than about 10% by weight of thefiller.
 45. The battery electrode of claim 29, wherein the first PTCfilm is formed by crosslinking a precursor of the crosslinked polymer inthe presence of barium titanate.
 46. The battery electrode of claim 29,wherein the first PTC film is formed using water as a solvent.
 47. Thebattery electrode of claim 29, wherein the first PTC film furthercomprises a fire retardant.
 48. The battery electrode of claim 29,further comprising: a current collector, a second electroactive layer,and a second PTC film—wherein the first PTC film or the second PTC filmis disposed on one side of the current collector such that at least onePTC film is in direct contact with the current collector, and whereinfirst electroactive layer or the second electroactive layer isinterposed between the first PTC film and the second PTC film such thatno PTC film is direct contact with another PTC film.
 49. A lithiumbattery comprising: an anode; a cathode; a separator; and electrolyte,wherein the anode and/or the cathode comprises the battery electrode ofclaim
 29. 50. The battery electrode of claim 29, further comprising afire-retardant material, wherein the fire retardant material comprisesan inorganic material adapted to release carbon dioxide; a borate;and/or an organophosphate.
 51. The battery electrode of claim 29,wherein the battery electrode includes a same number of the first PTCfilm as electroactive layers.